EP0011873B1 - Polyazo dyestuffs, their preparation and application to the dyeing of cellulose materials - Google Patents

Description

entsprechen, worin

• D Rest der Benzol- oder Naphthalinreihe,
• R, und R₂ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, C_I-C₄-Alkoxy, Halogen, Carboxy, Hydroxy, Acylamino wie Aminocarbonylamino und insbesondere C₁-C₄ -Alkylcarbonylamino, C₁-C₄-Alkyisulfonylami- no, Arylcarbonylamino, insbesondere Benzoylamino, Arylsulfonylamino, insbesondere Benzolsulfonylamino, Acyloxy, insbesondere C₁-C₄,-Alkyl- carbonyloxy oder Arylcarbonyloxy, insbesondere Benzoyloxy bedeuten,
• R₃ ein nicht faserreaktiver Substituent,
• n 0 oder 1 und
• m 0 oder 1 ist.

The present invention relates to new, metal-containing polyazo dyes which are in the form of the free acid of the formula (1)

correspond to what

• D rest of the benzene or naphthalene series,
• R, and R ₂ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C _I -C ₄ alkoxy, halogen, carboxy, hydroxy, acylamino such as aminocarbonylamino and in particular C ₁ -C ₄ alkylcarbonylamino, C ₁ -C ₄ - Alkyisulfonylamino, arylcarbonylamino, in particular benzoylamino, arylsulfonylamino, in particular benzenesulfonylamino, acyloxy, in particular C ₁ -C ₄ -alkylcarbonyloxy or arylcarbonyloxy, in particular benzoyloxy,
• R _{3 is} a non-fiber-reactive substituent,
• n 0 or 1 and
• m is 0 or 1.

The alkyl, alkoxy, aryl (especially phenyl) radicals can optionally be further substituted. The rest D may contain further azo groups, e.g. B. optionally substituted phenylazo or naphthylazo groups.

oder Gruppen -OR₃ oder -S-R₆, worin

• R₄ und R₅ unabhängig voneinander Wasserstoff, Amino, niedermolekulares Alkyl, Aryl, Aralkyl oder Cycloalkyl bedeuten oder zusammen, gegebenenfalls unter Einschluß eines oder mehrerer Heteroatome insbesondere Sauerstoff und/oder Stickstoff, einen Ring bilden, insbesondere einen 5-oder 6gliedrigen, und
• R₆ für Wasserstoff, niedermolekulares Alkyl, Aryl oder Aralkyl steht.

Suitable substituents R ₃ are, for example, amino groups such as

or groups -OR ₃ or -SR ₆ , wherein

• R ₄ and R ₅ independently of one another denote hydrogen, amino, low molecular weight alkyl, aryl, aralkyl or cycloalkyl or together, optionally including one or more heteroatoms, in particular oxygen and / or nitrogen, form a ring, in particular a 5-membered or 6-membered member, and
• R _{6 represents} hydrogen, low molecular weight alkyl, aryl or aralkyl.

The alkyl, aryl or aralkyl radicals can have customary substituents.

• N-Methyl-(2-hydroxyäthyl)-amino,
• Amino-, Methylamino-, Dimethylamino-,
• Äthylamino-, Diäthylamino-,
• 2-Hydroxyäthylamino-, Bis-(2-hydroxyäthyl)-amino-, Allylamino-, Diallylamino-,
• Methoxyäthylamino-, Sulfatoäthylamino-, Carboxymethylamino-, N-Methyl-
• N-carboxymethylamino-, Carboxyäthylamino-, N-Methyl-N-sulfomethylamino-,
• Sulfoäthylamino-N-methyl-N-sulfoäthylamino-, Cyclohexylamino-, Pyrrolidino-,
• Piperidino-, 1-Methylpiperazino-,
• Morpholino-, 4-Morpholinoamino-,
• Benzylamino-, gegebenenfalls substituiertes Phenyl- oder Naphthylamino.

Substituents R ₃ to be mentioned in particular are:

• N-methyl- (2-hydroxyethyl) amino,
• Amino, methylamino, dimethylamino,
• Ethylamino, diethylamino,
• 2-hydroxyethylamino, bis (2-hydroxyethyl) amino, allylamino, diallylamino,
• Methoxyethylamino, sulfatoethylamino, carboxymethylamino, N-methyl
• N-carboxymethylamino-, carboxyethylamino-, N-methyl-N-sulfomethylamino-,
• Sulfoethylamino-N-methyl-N-sulfoethylamino-, cyclohexylamino-, pyrrolidino-,
• Piperidino, 1-methylpiperazino,
• Morpholino, 4-morpholinoamino,
• Benzylamino, optionally substituted phenyl or naphthylamino.

worin

• D, R₁ R₂, R₄, R₅, m und n die vorstehend genannte Bedeutung haben.

Preferred dyes are those of the general formula (2)

wherein

• D, R ₁ R ₂ , R ₄ , R ₅ , m and n have the meaning given above.

• R₄, R₅ Wasserstoff oder C₁-C₄-Alkyl,
• R₄ Wasserstoff oder C₁-C₄-Alkyl und
• R₅ 2-Hydroxyäthyl,
• R₄, R₅ 2-Hydroxyäthyl.

Particularly preferred dyes are those of the general formula (2)

• R ₄ , R _{5 are} hydrogen or C ₁ -C ₄ alkyl,
• R _{4 is} hydrogen or C ₁ -C ₄ alkyl and
• R ₅ 2-hydroxyethyl,
• R ₄ , R ₅ 2-hydroxyethyl.

If D is a benzene radical, it can be, for example, sulfo, aminosulfonyl, carboxy, aminocarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen - especially chlorine, cyano, C _l -C ₄ alkylcarbonylamino, benzoylamino or hydroxy groups may be further substituted.

Naphthalene residues D can carry the azo bridge in the 1 or 2 position and are preferably substituted by C ₁ -C ₄ alkoxy, hydroxy and one to three sulfonic acid groups.

worin

• m 0 oder 1 ist,
• R₁ und R₂ die vorstehend genannte Bedeutung besitzen und
• D' wiederum einen Benzoyl- oder Naphthalinrest bedeutet, der wie oben genannt substituiert sein kann.

If D is a radical containing azo groups, it preferably corresponds in the form of the free acid to the general formula (3)

wherein

• m is 0 or 1,
• R ₁ and R _{2 have} the meaning given above and
• D 'in turn means a benzoyl or naphthalene residue which can be substituted as mentioned above.

mit 2-Amino-5-hydroxynaphthalin-4,8-disulfonsäure (5)

und mit einer Verbindung (6)

in beliebiger Reihenfolge zu einem Zwischenprodukt der Formel (7)

The polyazo dyes according to the invention are prepared, for example, by reacting a cyanuric halide with an azo dye of the formula (4) containing amino groups

with 2-amino-5-hydroxynaphthalene-4,8-disulfonic acid (5)

and with a connection (6)

in any order to an intermediate of formula (7)

The reaction takes place in 3 stages, the first at about 0-5 ° C, the second at about 35 to 40 ° C and the third at about 80-100 ° C and the resulting acid with alkaline agents such as. B. sodium acetate, sodium bicarbonate, soda, lithium carbonate, lithium hydroxide or sodium hydroxide is neutralized.

8-Amino-1-benzolsulfonyloxynaphthalin-5-sulfonsäure (9)

bzw. von 8-Amino-1-benzotsulfonyloxynaphthalin-3,6-disulfonsäure (10),

anschließender oxydativer Kupferung und Verseifung der o-Benzolsulfonylgruppe.It is advantageous to first react the component (4), (5) or (6) which carries the largest number of sulfo groups with the cyanuric halide. The dyes of the formula (1) are completed by diazotizing and coupling 8-amino-1-benzosulfonyloxynaphthalene-3,5-disulfonic acid (8),

8-amino-1-benzenesulfonyloxynaphthalene-5-sulfonic acid (9)

or 8-amino-1-benzotsulfonyloxynaphthalene-3,6-disulfonic acid (10),

subsequent oxidative coppering and saponification of the o-benzenesulfonyl group.

The production can be varied. It is possible, for example, to react a cyanuric halide in a third stage with a compound (6) HR ₃ only after coupling of the compound (8), (9) or (10) and oxidative coppering, i.e. before the saponification of the o-benzoyl suffonylester to make.

erfolgt nach bekannten Verfahren.The preparation of the azo dyes of the formula (4) or (4a) containing amino groups

takes place according to known methods.

bzw.

und Kuppeln auf ein Anilinderivat

gegebenenfalls auf die entsprechende w-Methansäure und anschließende Verseifung.For example, dyes of the formula (4) are obtained by diazotizing a compound

respectively.

and domes on an aniline derivative

optionally to the corresponding w-methanoic acid and subsequent saponification.

Dyes of the formula (4a) are obtained by diazotizing an aminomonoazo dye (3) and coupling onto an aniline derivative (t2), if appropriate onto the corresponding w-methanoic acid and then saponifying.

Further reaction steps such as sulfonation can be carried out after coupling and saponification of the ω-methanoic acid.

oder der Formel

diazotiert und auf Phenol- oder Naphtholderivate der Formel (15)

kuppelt, die Hydroxygruppe gegebenenfalls alkyliert und die Nitrogruppe reduziert bzw. die Acylaminogruppe verseift.Of course, the amino group-containing azo dyes of the formula (4) can also be obtained by using compounds of the formula (13)

or the formula

diazotized and on phenol or naphthol derivatives of the formula (15)

couples, the hydroxy group is optionally alkylated and the nitro group is reduced or the acylamino group is saponified.

bzw.

gegebenenfalls sulfiert, ferner diazotiert und auf Phenol- bzw. Naphthofderivate

kuppelt, die Hydroxygruppe gegebenenfalls alkyliert und die Nitrogruppe reduziert bzw. die Acylaminogruppe verseift.Dyes of the formula (4a) are also obtained by diazotizing compounds of the formula (13) or (14) and on aniline derivatives of the formula (12), if appropriate on the corresponding ω-methanoic acids, the aminomonoazo dyes

respectively.

optionally sulfonated, further diazotized and on phenol or naphthof derivatives

couples, the hydroxy group is optionally alkylated and the nitro group is reduced or the acylamino group is saponified.

Examples of suitable compounds of the formula (11) or (t 1 a) are:

• Aniline, 2-, 3- or 4-methylaniline,
• 2,3-, 2,5-, 2,6-, 3,4- or 3,5-dimethylaniline, 2-, 3- or 4-ethylaniline,
• 2-, 3- or 4-methoxyaniline,
• 4-ethoxyaniline, 2-, 3- or
• 4- (2-hydroxyethoxyj-aniline,
• 2-, 3- or 4- (2-methoxyethoxy) aniline,
• 2-, 3- or 4-chloroaniline,
• Aniline-2-, -3- or -4-sulfonic acid amide,
• Aniline-2-, -3- or -4-sulfonic acid methyl
• amide, aniline-2-, -3- or -4-sulfonic acid-
• dimethylamide, aniline-2-, -3- or
• -4-carboxylic acid, aniline-3,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid,
• Aniline-2-, -3- or -4-carboxamide,
• Aniline-2-, -3- or -4-carboxylic acid methyl or ethyl ester, 2-, 3- or 4-cyananiline,
• 2-, 3- or 4-hydroxyaniline,
• 3- or 4-acetyfaminoaniline,
• 3- or 4-aminophenylurea
• Aniline-2-, -3- or -4-sulfonic acid,
• Aniline-2,4-, -2,5- or 3,5-disuffonic acid,
• 4- or 5-chloroaniline-2-sulfonic acid,
• 4,6-dichloroaniline-2-sulfonic acid,
• 4- or 6-chloroaniline-3-sulfonic acid,
• 2-chloroaniline or 2,5-dichloroaniline-4-sulfonic acid, 4- or 5-sulfo-2-aminobenzoic acid, 4- (acetylamino- or
• Methyl- or methoxyl) -aniline-2-sulfonic acid, 3-acetylamino-aniline-2-sulfonic acid,
• 2- or 3-methylaniline-4-sulfonic acid,
• 2- (methyl- or methoxy) -aniline-3-sulfonic acid, 1-naphthylamine-2-, -3-, -4-, -5-,
• -6-, -7- or -8-sulfonic acid, _
• 2-naphthylamine-1, -5-, -6-, -7- or
• -8-sulfonic acid, 1-naphthylamine-2,4-,
• -3.6-, -3.7-, -3.8-, -4.6-, -4.7-, -4.8-,
• -5,7- or -6,8-disulfonic acid,
• 2-naphthylamine-1,5-, -3,6-, -3,7-, -4,8-,
• -5,7- or 6,8-disulfonic acid,
• 1-naphthylamine-2,4,6-, -2,4,7-, -3,6,8-or -4,6,8-trisulfonic acid,
• 2-naphthyramine-1,5,7-, -3,6,8- or 4,6,8-trisulfonic acid.

• Anilin, 2- oder 3-Methylanilin,
• 2-Äthylanitin, 2,3-, 2,5-, 2,6- oder
• 3,5-Dimethylanilin, 2- oder 3-Methoxy-oder Äthoxyanilin, 2-Methyl-5-methoxyanilin, 2-Methoxy-5-methylanilin,
• 2-Äthoxy-5-methylanilin,
• 2,5-Dimethoxy- oder -Diäthoxyanilin,
• 3-Acetylaminoanilin, 3-Ureidoanilirr,
• 3-Hydroxyacetylaminoanilin,
• 3-Acetylamino-6-methylanilin,
• 3-Acetylamino-6-methoxyanilin,
• 3-Ureido-6-methylanitin.

Suitable compounds of the formula (12) are:

• Aniline, 2- or 3-methylaniline,
• 2-ethylanitine, 2,3-, 2,5-, 2,6- or
• 3,5-dimethylaniline, 2- or 3-methoxy- or ethoxyaniline, 2-methyl-5-methoxyaniline, 2-methoxy-5-methylaniline,
• 2-ethoxy-5-methylaniline,
• 2,5-dimethoxy or diethoxy aniline,
• 3-acetylaminoaniline, 3-ureidoanilirr,
• 3-hydroxyacetylaminoaniline,
• 3-acetylamino-6-methylaniline,
• 3-acetylamino-6-methoxyaniline,
• 3-ureido-6-methylanitine.

• 4-Nitroanilin, 2-Chlor- oder
• 3-Chlor-4-nitroanilin-,
• 2,5-Dichlor- oder 2,6-Dichlor-4-nitroanilin, 4-Nitro-2-methylanilin,
• 5-Chlor-4-nitro-2-methylanilin,
• 2-Cyan-4-nitroanilin
• 4-Nitroanitinsulfonsäure-(2) oder -(3),
• 4-Nitroanilincarbonsäure-(2).

Suitable compounds of formula (13) are:

• 4-nitroaniline, 2-chloro or
• 3-chloro-4-nitroaniline,
• 2,5-dichloro- or 2,6-dichloro-4-nitroaniline, 4-nitro-2-methylaniline,
• 5-chloro-4-nitro-2-methylaniline,
• 2-cyan-4-nitroaniline
• 4-nitroanitinsulfonic acid- (2) or - (3),
• 4-nitroaniline carboxylic acid- (2).

• 4-Amino-acetanilid, 4-Amino-oxanilsäure,-
• 2,5-Dichlor-4-amino-acetanilid,
• 2-Amino-5-acetylaminotoluol,
• 5-Amino-2-oxalylamino-benzolsulfonsäure,
• 2-Amino-5-formylamino-benzolsulfonsäure,
• 2-Amino-5-acetylamino-benzolsulfonsäure,
• 2-Amino-5-acetylamino- benzolcarbonsäure.
• Phenol, 2-, 3- oder 4-Methylphenol, 1-Hydroxybenzol-2-carbonsäure,
• 2-, 3- oder 4-Chlorphenol,
• 2-Methyl-3-, -5- oder -6-chlorphenol,
• 3-Methyl-6-chlorphenol, 2-Äthylphenol,
• 2,3-, 2,5-, 2,6- oder 3,5-Dichlorphenol,
• 2,6-Diäthylphenol, 2-Methoxyphenol,
• 2-Äthoxyphenol, 3-Methoxyphenol,
• 3-Acetylaminophenol, 4-Hydroxydiphenyl,
• Phenolsulfonsäure-(2) und -(3),
• 1 - oder 2-Naphthol,
• 1-Naphthol-3-, -4- oder -5-sulfonsäure,
• 2-Naphthol-4-, -5-, -6- oder -7-sulfonsäure,
• 1-Naphthol-3,6-, -3,7-, -3,8-, -4,8- oder
• -5,7-disulfonsäure,
• 2-Naphthol-3,6-, -3,7-, -4,8-, 5,7- oder
• -6,8-disulfonsäure,
• 2-Hydroxynaphthoesäure-(3), -amid,
• -anilid, -chloranilid oder -toluidid.

Suitable compounds of the formula (14) are:

• 4-amino-acetanilide, 4-amino-oxanilic acid,
• 2,5-dichloro-4-aminoacetanilide,
• 2-amino-5-acetylaminotoluene,
• 5-amino-2-oxalylamino-benzenesulfonic acid,
• 2-amino-5-formylamino-benzenesulfonic acid,
• 2-amino-5-acetylamino-benzenesulfonic acid,
• 2-amino-5-acetylaminobenzenecarboxylic acid.
• Phenol, 2-, 3- or 4-methylphenol, 1-hydroxybenzene-2-carboxylic acid,
• 2-, 3- or 4-chlorophenol,
• 2-methyl-3-, -5- or -6-chlorophenol,
• 3-methyl-6-chlorophenol, 2-ethylphenol,
• 2,3-, 2,5-, 2,6- or 3,5-dichlorophenol,
• 2,6-diethylphenol, 2-methoxyphenol,
• 2-ethoxyphenol, 3-methoxyphenol,
• 3-acetylaminophenol, 4-hydroxydiphenyl,
• Phenolsulfonic acid- (2) and - (3),
• 1 - or 2-naphthol,
• 1-naphthol-3-, -4- or -5-sulfonic acid,
• 2-naphthol-4-, -5-, -6- or -7-sulfonic acid,
• 1-naphthol-3,6-, -3,7-, -3,8-, -4,8- or
• -5,7-disulfonic acid,
• 2-naphthol-3,6-, -3,7-, -4,8-, 5,7- or
• -6,8-disulfonic acid,
• 2-hydroxynaphthoic acid (3), amide,
• anilide, chloranilide or toluidide.

• Alkylhalogenide, Alkylsulfonate,
• Halogenhydrine, Alkylencyanide und Alkylenoxide.

Suitable alkylating agents for etherifying the phenolic OH groups are:

• Alkyl halides, alkyl sulfonates,
• Halohydrins, alkylene cyanides and alkylene oxides.

The dyes are separated from the aqueous solution by salting out and dried. Dark dye powders are obtained, the alkali salts of which dissolve very well in water with a green hue.

The new dyes dye cotton and regenerated cellulose in full shades. They raise very well and equalize very well. Their colorations show excellent lightfastness.

example 1

59 parts of the aminomonoazo dye obtained by diazotizing 44 parts of 2-naphthylamine-4,8-disulfonic acid and coupling to 28 parts of anilinomethanoic acid and subsequent saponification of the methanoic acid are dissolved neutral in 1000 parts of water and cooled to 0 ° C. with ice.

27 parts of cyanuric chloride - dissolved in acetone - are slowly added dropwise to the above solution. At the same time, a pH of 4-6 is maintained with dilute soda solution. Then 46 parts of 2-amino-5-hydroxynaphthalene-4,8-disulfonic acid dissolved in 200 parts of water are added until neutral, heated to 35-50 ° C. and kept at pH 6 with dilute soda solution. The reaction is complete after about 3 hours.

66 parts of 8-amino-1-benzenesulfonyloxynaphthalene-3,6-disulfonic acid are dissolved in 600 parts of water until neutral, cooled to 0 ° C. with ice and with 50 parts of hydrochloric acid (30% strength) and 40 parts of nitrite solution (30% strength) ) diazotized. The diazo solution thus obtained is slowly poured into the above solution and, at the same time, pH 7 is maintained with soda solution. The coupling is rapidly ended.

und färbt Baumwolle und Zellwolle grün.After adding 40 parts of copper sulfate, 400 parts of hydrogen peroxide solution (3%) are added dropwise in 1-2 hours. It is salted out and insulated. The oxidatively copper dyestuff paste is dissolved in 2000 parts of water until neutral, 20 parts of ethanolamine are added and the mixture is slowly warmed to 90-95 ° C. The reaction of the third halogen atom on the cyanuric chloride is complete after 1-2 hours. To saponify the o-benzenesulfonyl ester 5% sodium hydroxide solution (40%) was added and the mixture was stirred for a further 15 minutes at 90-95 C. The product was then salted out and filtered off with suction

and dyes cotton and rayon green.

Example 2

If in Example 1 the 8-amino-1-benzenesulfonyloxynaphthalene-3,6-disulfonic acid is replaced by the equivalent amount of 8-amino-1-benzenesulfonyloxynaphthalene-3,5-disulfonic acid, a dye is obtained, the cotton and Cellulose dyes in clear shades of green.

Example 3

If in Example 1 ethanolamine is replaced by the equivalent amount of diethanolamine or N-methylethanolamine, dyestuffs are obtained which turn cotton and rayon wool green.

Example 4

If in Example 1 ethanolamine is replaced by ammonia, a dye is obtained which dyes cotton and rayon green.

Example 5

If Example 2 ethanolamine is replaced by the equivalent amount of diethanolamine or N-methylethanolamine, dyestuffs are obtained which turn cotton or cotton wool green.

Example 6

Replacing ethanolamine with ammonia in Example 2 gives a dye which dyes cotton and rayon green.

in der Tabelle angegebenen Diazokomponenten A-NH₂, D-NH₂ bzw. NO₂-K-NH₂, die Kupplungskomponenten K-NH₂ bzw. D-OH sowie die Substituenten R₃-H verwendet.

Further dyes are obtained, the preparation of which takes place analogously to Example 1, if one follows the general formula

used in the table diazo components A-NH ₂ , D-NH ₂ or NO ₂ -K-NH ₂ , the coupling components K-NH ₂ or D-OH and the substituents R ₃ -H.

In the examples in Table I, 8-amino-1-hydroxynaphthalene-3,6-disuffonic acid is replaced by the equivalent amount of 8-amino-1-hydroxynaphthalene-3,5-disutonic acid or 8-amino-1-hydroxynaphthalene-5-sulfonic acid , this also results in valuable dyes that dye cotton in the specified tones.

If, in the examples in Table I, R ₃ -H is used N-methylethanolamine, valuable dyestuffs are also obtained which dye cotton in the specified tones.

Claims (8)

1. Metal-containing polyazo dyestuffs of the general formula

wherein

D denotes a radical of the benzene or naphthalene series,

R, and R₂ independently of one another denote hydrogen, C_l-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxyl, hydroxyl, acylamino or acyloxy,

R₃ is a substituent which is not fibre- reactive,

n is 0 or 1,

m is 0 or 1.

2. Dyestuffs according to Claim 1, wherein

R₃ is an amino group

or a group -O-R₆ or -S-R₆, wherein

R₄ and R₅ independently of one another denote hydrogen, amino, low-molecular alkyl, aryl, aralkyl or cycloalkyl, or together, optionally with the inclusion of one or more hetero-atoms, in particular oxygen and/or nitrogen, form a ring, in particular a 5-membered or 6-membered ring, and

R₆ represents hydrogen, low-molecular alkyl, aryl or aralkyl.

3. Dyestuffs according to Claims 1-2, wherein

R₄ and R₆ hydrogen or C_l-C₄-alkyl,

R₄ hydrogen or C₁-C₄-alkyl and

R₅ 2-hydroxyethyl, or

R₄ and R₅. 2_-hydroxyethyl.

4. Dyestuffs according to Claims 1-3, wherein D is a phenyl radical which can optionally be substituted by sulpho, aminosulphonyl, carboxyl, aminocarbonyl, C_l-C₄-alkoxycarbonyl, C₁-C₄- alkyl, C₁-C₄-alkoxy, halogen, in particular chlorine, cyano, C₁-C₄-alkylcarbonylamino, benzoylamino or hydroxyl.

5. Dyestuffs according to Claims 1-3, wherein D is a 1- or 2-naphthyl radical which contains 1 to 3 sulphonic acid groups and can be substituted by C₁-C₄-alkoxy and hydroxyl.

6. Dyestuffs according to Claims 1-3, wherein D denotes the radical of a monoazo dyestuff, of the general formula

wherein

m is 0 or 1,

R, and R₂ have the meaning given in Claim 1 and

D' is a phenyl or naphthyl radical according to Claims 4 or 5.

7. Process for the preparation of the metal-containing polyazo dyestuffs of Claim 1, characterised in that a cyanuric halide is reacted with an azo dyestuffs of the formula

with 2-amino-5-hydroxynaphthalene-4,8-disulphonic acid and with a compound R₃-H, in any desired sequence, a diazotised 8-amino-1-ben- zenesulphonyloxynaphthalene-5-sulphonic acid or -3,5- or -3,6-disulphonic acid is then coupled on, the coupling product is subject to oxidative coppering and the o-benzenesulphonyl ester group is saponified.

8. Use of the dyestuffs according to Claims 1-6 for dyeing materials containing hydroxyl groups, in particular textile materials.